This invention relates to improved photovoltaic effects in thin films of cuprous oxide on thin copper foil.
Photovoltaic generation of electric current has become a subject of great interest as increased attention has been given to means for the utilization of solar energy, specifically the generation of electricity from sunlight. Photovoltaic effects depend upon the development of semi-conductor PN junctions, which in turn depend upon the creation and stabilizing of electron holes in the selected lattice structure. In a commonly employed system, silicon crystals are doped with boron and with phosphorus atoms to produce, respectively, P-type material and N-type material. P-type material, due to an electron deficiency, attracts electrons and thus appears to act like a positive material. Conversely, N-type material, having a supply of free electrons, acts like a negative material. When P- and N-type materials are fused together, free electrons from the N-type material flow into the holes in the P-type material. The resulting PN junction provides the fundamental unit for the modern solar cell. Photovoltaic processes are not limited to single-crystal or polycrystalline silicon. Other common systems employ germanium, copper-cadmium sulfide, or gallium arsenide. Less common, but effective, systems employ cuprous oxide in contact with metallic copper. The cuprous oxide-copper system is an attractive one because of the lower materials cost but its use in solar cells has been limited because of poor efficiency.
In U.S. Pat. No. 3,398,028, Scott reported the formation of a cuprous oxide coating on copper by heating a copper base alloy to a temperature in the range 600.degree.-1050.degree. C. in an inert atmosphere and then cooling in an atmosphere containing a very limited proportion (about 0.0001%) of oxygen. Barnett, et al., U.S. Pat. No. 4,239,553 relates to solar cells comprising a copper sulfide absorber layer protected by a thin copper oxide layer, the entire system being encapsulated in glass for increased durability and maintenance of efficiency. In another solar cell, Rothwarf U.S. Pat. No. 4,267,398 provides a layer of copper oxide adjacent to the absorber material.
Photovoltaic properties of single-crystal and polycrystalline cuprous oxide-copper contacts were studied extensively by Assimos et al., J. Appl. Phys., vol. 44, pp. 1,687-1,693 (1973). Single-crystal cuprous oxide was reduced to metallic copper employing atomic hydrogen at room temperature. Polycrystalline contacts were prepared by partial oxidation of copper plate in air at 1000.degree. C. The copper plate was 2 mm. thick and the resulting oxide layer was 150 microns in thickness. Herion, Appl. Phys. Lett., vol. 34, pp. 599-601 (1979) oxidized a copper sheet (0.5 mm. thick) in air at 1050.degree. C. for 1 minute to obtain a cuprous oxide layer (20 microns thick) having very good adherence. Fortin et al., Can. J. Phys., vol. 60, pp. 901-908 (1982), prepared a 1-micron layer of cuprous oxide on a copper film (1 mm. thick) by employing a high oxygen pressure (50 Torr.) at 960.degree. C. for less than 1 second exposure time.
The process of this invention, employing very thin films of copper foil, surprisingly has produced unusually large photovoltaic effects, under process conditions not suggested by the prior art.